Dynamic shear modulus of isotropic elastomers

We have investigated the dynamic mechanical behavior of two cross-linked polymer networks with very different topologies: one made of backbones randomly linked along their length; the other with fixed-length strands uniformly cross-linked at their ends. The samples were analyzed using oscillatory shear, at very small strains corresponding to the linear regime. This was carried out at a range of frequencies, and at temperatures ranging from the glass plateau, through the glass transition, and well into the rubbery region. Through the glass transition, the data obeyed the time-temperature superposition principle, and could be analyzed using WLF treatment. At higher temperatures, in the rubbery region, the storage modulus was found to deviate from this, taking a value that is independent of frequency. This value increased linearly with temperature, as expected for the entropic rubber elasticity, but with a substantial negative offset inconsistent with straightforward enthalpic effects. Conversely, the loss modulus continued to follow time-temperature superposition, decreasing with increasing temperature, and showing a power-law dependence on frequency.

Water vapour self-continuum and water dimers: 1. Analysis of recent work

Recent laboratory observations and advances in theoretical quantum chemistry allow a reappraisal of the fundamental mechanisms that determine the water vapour self-continuum absorption throughout the infrared and millimetre wave spectral regions. By starting from a framework that partitions bimolecular interactions between water molecules into free-pair states, true bound and quasi-bound dimers, we present a critical review of recent observations, continuum models and theoretical predictions. In the near-infrared bands of the water monomer, we propose that spectral features in recent laboratory-derived self-continuum can be well explained as being due to a combination of true bound and quasi-bound dimers, when the spectrum of quasi-bound dimers is approximated as being double the broadened spectrum of the water monomer. Such a representation can explain both the wavenumber variation and the temperature dependence. Recent observations of the self-continuum absorption in the windows between these near-infrared bands indicate that widely used continuum models can underestimate the true strength by around an order of magnitude. An existing far-wing model does not appear able to explain the discrepancy, and although a dimer explanation is possible, currently available observations do not allow a compelling case to be made. In the 8–12 micron window, recent observations indicate that the modern continuum models either do not properly represent the temperature dependence, the wavelength variation, or both. The temperature dependence is suggestive of a transition from the dominance of true bound dimers at lower temperatures to quasibound dimers at higher temperatures. In the mid- and far-infrared spectral region, recent theoretical calculations indicate that true bound dimers may explain at least between 20% and 40% of the observed self-continuum. The possibility that quasi-bound dimers could cause an additional contribution of the same size is discussed. Most recent theoretical considerations agree that water dimers are likely to be the dominant contributor to the self-continuum in the mm-wave spectral range.

Summer drought in northern midlatitudes in a time-dependent CO2 climate experiment

A time-dependent climate-change experiment with a coupled ocean–atmosphere general circulation model has been used to study changes in the occurrence of drought in summer in southern Europe and central North America. In both regions, precipitation and soil moisture are reduced in a climate of greater atmospheric carbon dioxide. A detailed investigation of the hydrology of the model shows that the drying of the soil comes about through an increase in evaporation in winter and spring, caused by higher temperatures and reduced snow cover, and a decrease in the net input of water in summer. Evaporation is reduced in summer because of the drier soil, but the reduction in precipitation is larger. Three extreme statistics are used to define drought, namely the frequency of low summer precipitation, the occurrence of long dry spells, and the probability of dry soil. The last of these is arguably of the greatest practical importance, but since it is based on soil moisture, of which there are very few observations, the authors’ simulation of it has the least confidence. Furthermore, long time series for daily observed precipitation are not readily available from a sufficient number of stations to enable a thorough evaluation of the model simulation, especially for the frequency of long dry spells, and this increases the systematic uncertainty of the model predictions. All three drought statistics show marked increases owing to the sensitivity of extreme statistics to changes in their distributions. However, the greater likelihood of long dry spells is caused by a tendency in the character of daily rainfall toward fewer events, rather than by the reduction in mean precipitation. The results should not be taken as firm predictions because extreme statistics for small regions cannot be calculated reliably from the output of the current generation of GCMs, but they point to the possibility of large increases in the severity of drought conditions as a consequence of climate change caused by increased CO2.

Lag-time effects on a naturally ventilated large thermometer screen

Systematic natural ventilation effects on measured temperatures within a standard large wooden thermometer screen are investigated under summer conditions, using well-calibrated platinum resistance thermometers. Under low ventilation (2mwind speed u2 < 1.1 m s−1), the screen slightly underestimates daytime air temperature but overestimates air temperature nocturnally by 0.2◦C. The screen’s lag time L lengthens with decreasing wind speed, following an inverse power law relationship between L and u2. For u2 > 2 m s−1, L ∼ 2.5 min, increasing, when calm, to at least 15 min. Spectral response properties of the screen to air temperature fluctuations vary with wind speed because of the lag changes. Ventilation effects are particularly apparent at the higher (>25◦C) temperatures, both through the lag effect and from solar heating. For sites where wind speed decreases with increasing daytime temperature, thermometer screen temperatures may consequently show larger uncertainties at the higher temperatures. Under strong direct beam solar radiation (>850W m−2) the radiation effect is likely to be <0.4◦C. Copyright c 2011 RoyalMeteorological Society

On the evaluation of temperature trends in the tropical troposphere

A series of model experiments with the coupled Max-Planck-Institute ECHAM5/OM climate model have been investigated and compared with microwave measurements from the Microwave Sounding Unit (MSU) and re-analysis data for the period 1979–2008. The evaluation is carried out by computing the Temperature in the Lower Troposphere (TLT) and Temperature in the Middle Troposphere (TMT) using the MSU weights from both University of Alabama (UAH) and Remote Sensing Systems (RSS) and restricting the study to primarily the tropical oceans. When forced by analysed sea surface temperature the model reproduces accurately the time-evolution of the mean outgoing tropospheric microwave radiation especially over tropical oceans but with a minor bias towards higher temperatures in the upper troposphere. The latest reanalyses data from the 25 year Japanese re-analysis (JRA25) and European Center for Medium Range Weather Forecasts Interim Reanalysis are in very close agreement with the time-evolution of the MSU data with a correlation of 0.98 and 0.96, respectively. The re-analysis trends are similar to the trends obtained from UAH but smaller than the trends from RSS. Comparison of TLT, computed from observations from UAH and RSS, with Sea Surface Temperature indicates that RSS has a warm bias after 1993. In order to identify the significance of the tropospheric linear temperature trends we determined the natural variability of 30-year trends from a 500 year control integration of the coupled ECHAM5 model. The model exhibits natural unforced variations of the 30 year tropospheric trend that vary within ±0.2 K/decade for the tropical oceans. This general result is supported by similar results from the Geophysical Fluid Dynamics Laboratory (GFDL) coupled climate model. Present MSU observations from UAH for the period 1979–2008 are well within this range but RSS is close to the upper positive limit of this variability. We have also compared the trend of the vertical lapse rate over the tropical oceans assuming that the difference between TLT and TMT is an approximate measure of the lapse rate. The TLT–TMT trend is larger in both the measurements and in the JRA25 than in the model runs by 0.04–0.06 K/decade. Furthermore, a calculation of all 30 year TLT–TMT trends of the unforced 500-year integration vary between ±0.03 K/decade suggesting that the models have a minor systematic warm bias in the upper troposphere.

Effects of polydispersity on the order-disorder transition of diblock copolymer melts

The effect of polydispersity on an AB diblock copolymer melt is investigated using latticebased Monte Carlo simulations. We consider melts of symmetric composition, where the B blocks are monodisperse and the A blocks are polydisperse with a Schultz-Zimm distribution. In agreement with experiment and self-consistent field theory (SCFT), we find that polydispersity causes a significant increase in domain size. It also induces a transition from flat to curved interfaces, with the polydisperse blocks residing on the inside of the interfacial curvature. Most importantly, the simulations show a relatively small shift in the order-disorder transition (ODT) in agreement with experiment, whereas SCFT incorrectly predicts a sizable shift towards higher temperatures.

Monte Carlo phase diagram for a polydisperse diblock copolymer melt

The phase diagram for an AB diblock copolymer melt with polydisperse A blocks and monodisperse B blocks is evaluated using lattice-based Monte Carlo simulations. Experiments on this system have shown that the A-block polydispersity shifts the order-order transitions (OOTs) towards higher A-monomer content, while the order-disorder transition (ODT) moves towards higher temperatures when the A blocks form the minority domains and lower temperatures when the A blocks form the matrix. Although self-consistent field theory (SCFT) correctly accounts for the change in the OOTs, it incorrectly predicts the ODT to shift towards higher temperatures at all diblock copolymer compositions. In contrast, our simulations predict the correct shifts for both the OOTs and the ODT. This implies that polydispersity amplifies the fluctuation-induced correction to the mean-field ODT, which we attribute to a reduction in packing frustration. Consistent with this explanation, polydispersity is found to enhance the stability of the perforated-lamellar phase.

Effect of elevated CO2 and high temperature on seed-set and grain quality of rice

Hybrid vigour may help overcome the negative effects of climate change in rice. A popular rice hybrid (IR75217H), a heat-tolerant check (N22), and a mega-variety (IR64) were tested for tolerance of seed-set and grain quality to high-temperature stress at anthesis at ambient and elevated [CO2]. Under an ambient air temperature of 29 °C (tissue temperature 28.3 °C), elevated [CO2] increased vegetative and reproductive growth, including seed yield in all three genotypes. Seed-set was reduced by high temperature in all three genotypes, with the hybrid and IR64 equally affected and twice as sensitive as the tolerant cultivar N22. No interaction occurred between temperature and [CO2] for seed-set. The hybrid had significantly more anthesed spikelets at all temperatures than IR64 and at 29 °C this resulted in a large yield advantage. At 35 °C (tissue temperature 32.9 °C) the hybrid had a higher seed yield than IR64 due to the higher spikelet number, but at 38 °C (tissue temperature 34–35 °C) there was no yield advantage. Grain gel consistency in the hybrid and IR64 was reduced by high temperatures only at elevated [CO2], while the percentage of broken grains increased from 10% at 29 °C to 35% at 38 °C in the hybrid. It is concluded that seed-set of hybrids is susceptible to short episodes of high temperature during anthesis, but that at intermediate tissue temperatures of 32.9 °C higher spikelet number (yield potential) of the hybrid can compensate to some extent. If the heat tolerance from N22 or other tolerant donors could be transferred into hybrids, yield could be maintained under the higher temperatures predicted with climate change.

How will organic carbon stocks in mineral soils evolve under future climate? Global projections using RothC for a range of climate change scenarios

We use a soil carbon (C) model (RothC), driven by a range of climate models for a range of climate scenarios to examine the impacts of future climate on global soil organic carbon (SOC) stocks. The results suggest an overall global increase in SOC stocks by 2100 under all scenarios, but with a different extent of increase among the climate model and emissions scenarios. The impacts of projected land use changes are also simulated, but have relatively minor impacts at the global scale. Whether soils gain or lose SOC depends upon the balance between C inputs and decomposition. Changes in net primary production (NPP) change C inputs to the soil, whilst decomposition usually increases under warmer temperatures, but can also be slowed by decreased soil moisture. Underlying the global trend of increasing SOC under future climate is a complex pattern of regional SOC change. SOC losses are projected to occur in northern latitudes where higher SOC decomposition rates due to higher temperatures are not balanced by increased NPP, whereas in tropical regions, NPP increases override losses due to higher SOC decomposition. The spatial heterogeneity in the response of SOC to changing climate shows how delicately balanced the competing gain and loss processes are, with subtle changes in temperature, moisture, soil type and land use, interacting to determine whether SOC increases or decreases in the future. Our results suggest that we should stop looking for a single answer regarding whether SOC stocks will increase or decrease under future climate, since there is no single answer. Instead, we should focus on improving our prediction of the factors that determine the size and direction of change, and the land management practices that can be implemented to protect and enhance SOC stocks.

Cultivating C4 crops in a changing climate: sugarcane in Ghana

Over the next few decades, it is expected that increasing fossil fuel prices will lead to a proliferation of energy crop cultivation initiatives. The environmental sustainability of these activities is thus a pressing issue—particularly when they take place in vulnerable regions, such as West Africa. In more general terms, the effect of increased CO2 concentrations and higher temperatures on biomass production and evapotranspiration affects the evolution of the global hydrological and carbon cycles. Investigating these processes for a C4 crop, such as sugarcane, thus provides an opportunity both to extend our understanding of the impact of climate change, and to assess our capacity to model the underpinning processes. This paper applies a process-based crop model to sugarcane in Ghana (where cultivation is planned), and the São Paulo region of Brazil (which has a well-established sugarcane industry). We show that, in the Daka River region of Ghana, provided there is sufficient irrigation, it is possible to generate approximately 75% of the yield achieved in the São Paulo region. In the final part of the study, the production of sugarcane under an idealized temperature increase climate change scenario is explored. It is shown that doubling CO2 mitigates the degree of water stress associated with a 4 °C increase in temperature.

Climate-related changes in peatland carbon accumulation during the last millennium.

Peatlands are a major terrestrial carbon store and a persistent natural carbon sink during the Holocene, but there is considerable uncertainty over the fate of peatland carbon in a changing climate. It is generally assumed that higher temperatures will increase peat decay, causing a positive feedback to climate warming and contributing to the global positive carbon cycle feedback. Here we use a new extensive database of peat profiles across northern high latitudes to examine spatial and temporal patterns of carbon accumulation over the past millennium. Opposite to expectations, our results indicate a small negative carbon cycle feedback from past changes in the long-term accumulation rates of northern peatlands. Total carbon accumulated over the last 1000 yr is linearly related to contemporary growing season length and photosynthetically active radiation, suggesting that variability in net primary productivity is more important than decomposition in determining long-term carbon accumulation. Furthermore, northern peatland carbon sequestration rate declined over the climate transition from the Medieval Climate Anomaly (MCA) to the Little Ice Age (LIA), probably because of lower LIA temperatures combined with increased cloudiness suppressing net primary productivity. Other factors including changing moisture status, peatland distribution, fire, nitrogen deposition, permafrost thaw and methane emissions will also influence future peatland carbon cycle feedbacks, but our data suggest that the carbon sequestration rate could increase over many areas of northern peatlands in a warmer future.

The impact of monsoon intraseasonal variability on renewable power generation in India

India is increasingly investing in renewable technology to meet rising energy demands, with hydropower and other renewables comprising one-third of current installed capacity. Installed wind-power is projected to increase 5-fold by 2035 (to nearly 100GW) under the International Energy Agency’s New Policies scenario. However, renewable electricity generation is dependent upon the prevailing meteorology, which is strongly influenced by monsoon variability. Prosperity and widespread electrification are increasing the demand for air conditioning, especially during the warm summer. This study uses multi-decadal observations and meteorological reanalysis data to assess the impact of intraseasonal monsoon variability on the balance of electricity supply from wind-power and temperature-related demand in India. Active monsoon phases are characterised by vigorous convection and heavy rainfall over central India. This results in lower temperatures giving lower cooling energy demand, while strong westerly winds yield high wind-power output. In contrast, monsoon breaks are characterised by suppressed precipitation, with higher temperatures and hence greater demand for cooling, and lower wind-power output across much of India. The opposing relationship between wind-power supply and cooling demand during active phases (low demand, high supply) and breaks (high demand, low supply) suggests that monsoon variability will tend to exacerbate fluctuations in the so-called demand-net-wind (i.e., electrical demand that must be supplied from non-wind sources). This study may have important implications for the design of power systems and for investment decisions in conventional schedulable generation facilities (such as coal and gas) that are used to maintain the supply/demand balance. In particular, if it is assumed (as is common) that the generated wind-power operates as a price-taker (i.e., wind farm operators always wish to sell their power, irrespective of price) then investors in conventional facilities will face additional weather-volatility through the monsoonal impact on the length and frequency of production periods (i.e. their load-duration curves).

Functionality of lipase and emulsifiers in low-fat cakes with inulin

The functional effects of lipase (0.003 and 0.006 g/100 g of flour) and emulsifier (0.5 and 1 g/100 g of flour) on fat-replaced (0%, 50% and 70%) batters and cakes with inulin (0, 7.5 and 10 g/100 g/of flour, respectively) were studied. Emulsifier addition significantly lowered the relative density of the batter. Emulsifier incorporation increased the viscoelastic properties of the batter. In contrast, lipase incorporation decreased the degree of system structuring. The evolution of the dynamic moduli and complex viscosity with rising temperatures were studied. Batters with 1 g/100 g emulsifier displayed a significantly lower complex viscosity during heating, resulting in collapsed cakes. Differential scanning calorimetry results revealed that the thermal setting in the control cakes occurred at higher temperatures, and accordingly, greater cake expansion was observed. Cakes with 0.003 g/100 g lipase or 0.5 g/100 g emulsifier displayed volume and crumb cell structure that were similar to those of control cakes. Higher concentrations of both improvers gave rise to cakes with lower volume, higher hardness and lower springiness. During storage time, cakes with lipase displayed lower hardness. Both improvers, at low concentrations, could improve certain physical characteristics, such as crumb structure, of fat-replaced cakes with inulin.

The atomic structure of low-index surfaces of the intermetallic compound InPd

The intermetallic compound InPd (CsCl type of crystal structure with a broad compositional range) is considered as a candidate catalyst for the steam reforming of methanol. Single crystals of this phase have been grown to study the structure of its three low-index surfaces under ultra-high vacuum conditions, using low energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). During surface preparation, preferential sputtering leads to a depletion of In within the top few layers for all three surfaces. The near-surface regions remain slightly Pd-rich until annealing to ∼580 K. A transition occurs between 580 and 660 K where In segregates towards the surface and the near-surface regions become slightly In-rich above ∼660 K. This transition is accompanied by a sharpening of LEED patterns and formation of flat step-terrace morphology, as observed by STM. Several superstructures have been identified for the different surfaces associated with this process. Annealing to higher temperatures (≥750 K) leads to faceting via thermal etching as shown for the (110) surface, with a bulk In composition close to the In-rich limit of the existence domain of the cubic phase. The Pd-rich InPd(111) is found to be consistent with a Pd-terminated bulk truncation model as shown by dynamical LEED analysis while, after annealing at higher temperature, the In-rich InPd(111) is consistent with an In-terminated bulk truncation, in agreement with density functional theory (DFT) calculations of the relative surface energies. More complex surface structures are observed for the (100) surface. Additionally, individual grains of a polycrystalline sample are characterized by micro-spot XPS and LEED as well as low-energy electron microscopy. Results from both individual grains and “global” measurements are interpreted based on comparison to our single crystals findings, DFT calculations and previous literature.

Equilibrium behavior of symmetric ABA triblock copolymer melts

Melts of ABA triblock copolymer molecules with identical end blocks are examined using self-consistent field theory (SCFT). Phase diagrams are calculated and compared with those of homologous AB diblock copolymers formed by snipping the triblocks in half. This creates additional end segments which decreases the degree of segregation. Consequently, triblock melts remain ordered to higher temperatures than their diblock counterparts. We also find that middle-block domains are easier to stretch than end-block domains. As a result, domain spacings are slightly larger, the complex phase regions are shifted towards smaller A-segment compositions, and the perforated-lamellar phase becomes more metastable in triblock melts as compared to diblock melts. Although triblock and diblock melts exhibit very similar phase behavior, their mechanical properties can differ substantially due to triblock copolymers that bridge between otherwise disconnected A domains. We evaluate the bridging fraction for lamellar, cylindrical, and spherical morphologies to be about 40%–45%, 60%–65%, and 75%–80%, respectively. These fractions only depend weakly on the degree of segregation and the copolymer composition.